1,2-Dichlorobenzene → (1S,2S,3S,4R,5S)-5-[4-chloro-3-[[4-(2,2,2-trifluoroethoxy)phenyl]methyl]phenyl]-1-(hydroxymethyl)-6,8-dioxabicyclo[3.2.1]octane-2,3,4-triol

HRID 1913056ノート

反応式

HRID 1913056 の反応式
C([O:8][C@H:9]1[C@H:15]([O:16]CC2C=CC=CC=2)[C@@H:14]([O:24]CC2C=CC=CC=2)[C@:13]2([C:33]3[CH:38]=[CH:37][C:36]([Cl:39])=[C:35]([CH2:40][C:41]4[CH:46]=[CH:45][C:44]([O:47][CH2:48][C:49]([F:52])([F:51])[F:50])=[CH:43][CH:42]=4)[CH:34]=3)[O:32][C@@:10]1([CH2:53][OH:54])[CH2:11][O:12]2)C1C=CC=CC=1.ClC1C=CC=CC=1Cl>[Pd]>[Cl:39][C:36]1[CH:37]=[CH:38][C:33]([C@@:13]23[O:32][C@@:10]([CH2:53][OH:54])([CH2:11][O:12]2)[C@@H:9]([OH:8])[C@H:15]([OH:16])[C@H:14]3[OH:24])=[CH:34][C:35]=1[CH2:40][C:41]1[CH:46]=[CH:45][C:44]([O:47][CH2:48][C:49]([F:51])([F:50])[F:52])=[CH:43][CH:42]=1

参加物

4

反応物 2

HCID 72391,2-DichlorobenzeneHCID 86685153[(1S,2S,3S,4R,5S)-2,3,4-tribenzyloxy-5-[4-chloro-3-[[4-(2,2,2-trifluoroethoxy)phenyl]methyl]phenyl]-6,8-dioxabicyclo[3.2.1]octan-1-yl]methanol

生成物 1

HCID 86685154(1S,2S,3S,4R,5S)-5-[4-chloro-3-[[4-(2,2,2-trifluoroethoxy)phenyl]methyl]phenyl]-1-(hydroxymethyl)-6,8-dioxabicyclo[3.2.1]octane-2,3,4-triol収率 61.1%

試薬・触媒・溶媒 1

HCID 23938Palladium触媒

実験手順

[(1S,2S,3S,4R,5S)-2,3,4-tribenzyloxy-5-[4-chloro-3-[[4-(2,2,2-trifluoroethoxy)phenyl]methyl]phenyl]-6,8-dioxabicyclo[3.2.1]octan-1-yl]methanol 7m (20 mg, 0.03 mmol) was dissolved in 10 mL of mixed solution (THF and MeOH, v:v=1:1), followed by addition of o-dichlorobenzene (31 μL, 0.27 mmol) and Palladium/carbon (20 mg, 10%) in turn. The mixture was exchanged with H2 three times and was stirred for 2 hours. Thereafter, the reaction mixture was filtered. The filtrate was concentrated under reduced pressure and the resulting residue was purified by thin layer chromatography with developing solvent system A to obtain the title compound (1S,2S,3S,4R,5S)-5-[4-chloro-3-[[4-(2,2,2-trifluoroethoxy)phenyl]methyl]phenyl]-1-(hydroxymethyl)-6,8-dioxabicyclo[3.2.1]octane-2,3,4-triol 7 (9 mg, white solid), yield: 69.2%. MS m/z (ESI): 491.1 [M+1]; 1H NMR (400 MHz, CD3OD): δ 7.48 (m, 1H), 7.40-7.38 (m, 2H), 7.18-7.16 (d, 2H), 6.93-6.91 (d, 2H), 4.51-4.45 (q, 2H), 4.17-4.15 (d, 1H), 4.08 (s, 2H), 3.81-3.78 (d, 1H), 3.78-3.71 (d, 1H), 3.69-3.67 (m, 2H), 3.62-3.57 (m, 2H).

後処理

  1. filtrationThereafter, the reaction mixture was filtered
  2. concentrationThe filtrate was concentrated under reduced pressure
  3. customthe resulting residue was purified by thin layer chromatography with developing solvent system

出典と根拠

ORDレコード
ord-acbce858e82549a587cd56a51ff70189
出典データセット
uspto-grants-2013_12
特許番号
US08609622B2

反応ノート

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